JPH03200813A - Syndiotactic polypropylene copolymer - Google Patents

Abstract

PURPOSE:To obtain a syndiotactic polypropylene copolymer of an excellent balance of impact resistance and good transparency by incorporating an olefin other than propylene in an amount in a specified range. CONSTITUTION:A syndiotactic polypropylene copolymer, wherein the intensity of a peak observed at about 20.2ppm when measured by <13>C-NMR is at least 0.3 time larger than the intensity of a peak assignable to the methyl groups of the total propylene units, and 0.1-30mol% olefin other than propylene (2 C or 4-25C alpha-olefins can be used) is contained. The above polymer is a copolymer having an excellent balance between impact resistance and other properties and good transparency. An example of the catalyst system suitable for the production of this copolymer is a combination of a transition metal catalyst such as isopropyl(cyclopentadienyl-1-fluorenyl)zirconium dichloride with methylaluminoxane of a degree of polymerization of 10 or more.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to copolymers of syndiotactic polypropylene. Specifically, the present invention relates to a copolymer of propylene and other olefins having high syndiotacticity.

[Prior art]

The existence of syndiotactic polypropylene has been known for a long time, but the conventional low-temperature polymerization method using a catalyst consisting of a vanadium compound, ether, and organoaluminum has poor syndiotacticity, and the characteristics of syndiotactic polypropylene have not been fully realized. Furthermore, it is difficult to say that the copolymer of α-olefin and propylene is crystalline polypropylene.On the other hand, J, ^, EWEN et al. The syndiotactic pentad fraction is 0.7 due to the transition metal catalyst and the alumituxane catalyst.
It was discovered for the first time that it was possible to obtain polypropylene with good toughness exceeding
es, Soc, 1988, 110.6255-625
6).

[11113 to be solved by the invention] The method by J, ^, EHEN et al. has good activity per transition metal, and the obtained polymer has high toughness, and the physical properties of the polymer are relatively well-balanced. However, there were problems in that the transparency of the molded product was poor and the impact resistance was insufficient.

(Means for Solving !III) The present inventors solved the above !III by searching intensively for syndiotactic polypropylene having excellent balance of impact resistance and good transparency, and completed the present invention. , the present invention provides that the intensity of the peak observed at about 20.2 pp- measured by C-NMR is 0.3 or more of the intensity of the peak attributed to the methyl group of all propylene units, and 0.1
It is a syndiotactic polypropylene copolymer containing ~30 moles χ of olefins other than propylene.

Examples of the catalyst used for producing the propylene copolymer of the present invention include the compounds described in the above-mentioned documents.
When a propylene homopolymer is produced even if it has a different structure, the syndiotactic pentad fraction of the resulting polymer (^, Zambelli et al.
les vol 6687 (1973L vol 89
25 (1975)) Any catalyst system can be used as long as it provides a polymer with a relatively high toughness of about 0.7 or more; for example, a catalyst system consisting of a transition metal compound having an asymmetrical ligand and aluminoxane can be used. Catalytic systems are effective.

Catalyst systems suitable for producing the copolymer of the present invention include:
Examples of the aluminoxane include inpropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride and isopropyl (cyclopentajenyl-1-fluorenyl) zirconium dichloride described in the above literature. is a hydrocarbon residue having 1 to 3 carbon atoms, and compounds represented by the following are exemplified, and in particular, those in which R is a methyl group, methylaltuxane, and n is 5 or more, preferably 10 or more are used. The ratio of aluminoxane to the transition metal catalyst used is 10 to 1,000,000 moles, usually 50 to 500 moles. Besides these catalyst systems,
Compounds of alkylated transition metal catalysts and boron (for example, JP-A-1-501950, JP-A-1-502036)
etc.) can be used.

In the present invention, as the olefin other than propylene, α-olefins having 2 or 4 to 25 carbon atoms can be used, and in addition to ethylene, those having the general formula LC-C1l-(CIlg)-CHz (where n is 1 to
22) α-olefin represented by -(C11□)
, C113 group replaced with a branched alkyl group, such as 3-methylbutene-1,4-methylpentene-1,4,
Examples include branched α-olefins such as 4-dimethylpentene-1. It is also possible to use two or more of these α-olefins together, and the total amount is 0.1 to 3.
It is sufficient if it is 0 mol2.

There are no particular restrictions on the polymerization conditions, and solvent polymerization using an inert medium, bulk polymerization without an inert medium, or gas phase polymerization can also be used.The polymerization temperature is -100 to 200"C1. Polymerization pressure is normal pressure ~
It is common to carry out at 100 kg/d. Preferably the temperature is -100 to 100°C and normal pressure to 50 kg/CIi.

What is important in the present invention is to control the amount of monomers introduced into the polymerization system so that the proportion of α-olefin other than propylene in the total polymer is 0.1 to 30 mol χ;
And about 20.2p measured by C-NMR of the copolymer.
The above ratio is increased by washing with a hydrocarbon solvent as necessary so that the intensity of the peak observed in pm is 0.3 or more of the intensity of the peak attributed to the methyl group of all propylene units. If this ratio is less than 0.3, there will be problems such as the surface of the molded product becoming sticky. A peak measured based on silane and attributed to the methyl group of the propylene unit is observed at about 19 to 22 pp-.

If the proportion of other α-olefins other than propylene is less than 0.1 mol X, the impact resistance and transparency of the polymer will be poor, and if it is more than 30 mol X, the rigidity will be poor. Considering the balance between rigidity, impact resistance, and transparency, the content of other α-olefins is preferably about 0.2 to 30 mol 2 .

In the present invention, the molecular weight of the copolymer is not particularly limited as long as it can be used as a normal polymer, but from the point of view of use as a molding resin, the intrinsic viscosity measured in a tetralin solution at 135°C is 0. 05 or more, and the number average molecular weight in terms of propylene measured by Gelper ξ Ashin chromatography is about 1000 or more.

〔Example〕

The present invention will be further explained with reference to Examples below.

Example 1 Isopropyl(cyclopentadienyl-■-fluorenyl)zirconium dichloride obtained by lithiation of isopropylcyclopentagenyl-1-fluorene synthesized according to a conventional method in an autoclave with an internal volume of 2Il and reacting with zirconium tetrachloride. 51mg of methylaltoxane with a degree of polymerization of about 15 obtained by reacting hydrated copper sulfate and trimethylaluminum in toluene.
Dissolve 7 in toluene 11, add 2 kg/cii-G of propylene at 30''C, and then add 1.0 g of ethylene.
/aein for 1 minute every 10 minutes, and propylene was added so that the polymerization pressure was 2 kg/cd-G.
After 0 hours of polymerization, unreacted monomers were purged and filtered, and the resulting powder was washed 5 times with 1ffi toluene and dried under reduced pressure at 80'C to obtain 32 g of polymer. According to 13C-NMR analysis, what is the ethylene content? , 4wtX (10.7 mol χ), approximately 20.2pp
The ratio of the peak intensity observed at m to the total peak intensity observed at about 19 to 22 pps+ was 0.89. In addition, the intrinsic viscosity (hereinafter referred to as η) measured with a tetralin solution at 135°C was 1.26.
．． 2. Ratio of weight average molecular weight and number average molecular weight measured in 4-trichlorobenzene solution (hereinafter referred to as MW/MN)
was 2.2. This powder was press-molded at 210°C to produce a 1 mm sheet, and the following physical properties were measured.

・Bending rigidity: kg/ai ASfMO747 (
23℃)・Tensile yield strength: kg/c4 ASTM
D63B (23°C)・Elongation:%
ASTM D63B (23℃) / Izot (
(With notch) Impact strength: kg・cm/c+iASTM D
256 (23℃, -10℃)・Haze:% AST
Compliant with M 01003.

Bending rigidity is 2800kg/cj, tensile yield strength is 20
0kg/cj, what is the growth? 73L Izot impact strength is 68.2゜1 (23℃ and -10℃, respectively) kg-c
-7 cm, and haze was 44%.

Comparative Example 1 The physical properties were measured in the same manner as in Example 1 except that the polymerization was performed without using ethylene.
．． 1, the bending rigidity is 4700 kg/cj, the tensile yield strength is 224 kg/C4, the elongation is 740 L, and the Fizot impact strength is 14.1.2.1 (23℃, -
10℃) kg-cm/cs+, and haze is 68
! Met.

Example 2 1500 g of propylene was placed in an autoclave with an internal volume of 52 mm, and 10 mg of isopropyl (cyclopentadienyl-1 fluorenyl) zirconium dichloride and a polymerization degree of approximately 15 were added.
1.34 g of methylaluminoxane was injected at 30°C. Stir at 30°C for 1 hour while inserting 2 g of ethylene every 10 minutes. Then, after purging unreacted propylene, the powder was taken out and dispersed in 500 m of hexane.
The mixture was filtered at 0°C, washed three times with 500ml of hexane, and then dried under reduced pressure at 80°C to obtain 145g of syndiotactic polypropylene. Physical properties were measured in the same manner as in Example 1. 7) 77 was 1.33, ethylene content? , 5wt
N 2.3, bending rigidity is 2100 kg/cd, tensile yield strength is 200 kg/d, elongation is 820x, and Izot impact strength is 78.3.2 (23℃, -10 respectively)
'C) kg °c-/csb i? Ah, the haze was 38X.

Comparative Example 2 Physical properties were measured in the same manner as in Example 2 except that polymerization was performed without using ethylene. η was 1.26, the ratio of syndiotactic pentad was o, 93, and ■/MN was 2.
1, the bending rigidity is 5200 kg/ai, the tensile yield strength is 223 kg/cj, the elongation is 785
0°C) kg °cm/c-, and the haze was 62.

Example 3 Using an autoclave with an internal volume of 21 kg, the catalyst of Example 1 was used in the same manner as toluene 1 j! Dissolved in propylene at 30℃
5 kg/ci-G was inserted, then 45 g of butene-1 was injected, and propylene was added so that the polymerization pressure was 5 kg/d-G and polymerized for 2 hours. After polymerization, unreacted monomers were purged. The powder obtained is 1J of toluene! After washing 5 times with
g of polymer was obtained. "As analyzed by C-NMR, the butene-1 content was 15.1 wtX (11.8 mol2), about 1 of the peak intensity observed at about 20.2 ppm.
The ratio of the peak intensity observed between 9 and 22 pp- to the total was 0.84. Also, η is 1.23,
MW/)IN was 2.1. The crystallization temperature measured by differential scanning calorimetry as the peak temperature when melting at 140″C and cooling at 10°C is 75.6°C;
The melting point when heated was 121.130°C. This powder was shaped in the same manner as in Example 1 and its physical properties were measured.
Bending rigidity is 5100kg/cj, tensile yield strength is 24
3kg/cj, elongation is 763χ, Izod impact strength is 67.2.8 (23℃, -10℃, respectively) kg-c
m/cm, and the haze was 52.6X.

Example 4 1500 g of propylene was placed in an autoclave with an internal volume of 51.
Add 1200 g of butene and add 30 g of the same catalyst as in Example 2.
It was press-fitted at ℃. After stirring for 2 hours, unreacted propylene was purged, the powder was taken out, and hexane 500
The polymer was dispersed in -, filtered at 40°C, washed three times with 500 d of hexane, and then dried under reduced pressure at 80°C to obtain 148 g of a polymer insoluble in hexane. Physical properties were measured in the same manner as in Example 1, and η was 1.33, butene-1
Content 21.5wtX (17.0mol, approx. 20.2pp
The ratio of the peak intensity observed at - to the total peak intensity observed at about 19 to 22 ppm was 0.81. Further, the crystallization temperature measured by differential scanning calorimetry was 72.3°C, the melting point was 12B, 5.119.5°C, and the ratio/MN was 2.2. Perform this powder N
The 0 bending rigidity, which was molded in the same manner as L and measured the physical properties, was 55.
00kg/C4, tensile yield strength is 254kg/cm, elongation is 780X, 7 (Schiff) impact strength is 66.3.2 (
(23℃ and -1O℃, respectively) kg -cm/cm, and the haze is 42.3! Met.

Example 5 Using an autoclave with an internal volume of 21, the catalyst used in Example 1 was replaced with toluene lj! 3 kg/d-G of propylene was added at 30°C, and then 68 g of 4-methylpentene-1 was introduced under pressure, and the polymerization pressure of propylene was 3 kg.
/cj-G was added and polymerized for 1 hour. After 0 polymerization, unreacted monomer was purged and filtered. The powder obtained was washed 5 times with toluene 11 and dried under reduced pressure at 80°C to give 70g. Analysis by C-NMR revealed that 6.4wtX of 4-methylpentene-1 was obtained.
(3.3 mol X), and the ratio of the peak intensity observed at about 20.2 pp- to the total peak intensity observed at about 19-22 pp- was 0.88. Further, η was 1.05, and Q/MW was 2.0.

This powder was molded in the same manner as in Example 1, and its physical properties were measured.The zero bending rigidity was 2700 kg/cIi, the tensile yield strength was 129 kg/d, the elongation was 636, and the Izot impact strength was 58.4.3. 4 (23℃, -10℃, respectively)
Cl1l/Ca+, and haze was 28%.

Example 6 1000 g of propylene was placed in an autoclave with an internal volume of 51.
300 g of 4-methylpentene-1 was press-injected, a catalyst was inserted in the same manner as in Example 2, and the mixture was stirred at 30°C for 1 hour. After purging unreacted propylene, the powder was taken out, dispersed in 500 Jd of hexane, and filtered at 40°C. And another 50
Syndiotactic polypropylene 150 was washed 3 times with 0jd of hexane and then dried under reduced pressure at 80°C.
I got g. When physical properties were measured in the same manner as in Example 1, η was 0.98.4-methylpentene-1 content 12.5χ (6
, 7 mol χ), the ratio of the peak intensity observed at about 20.2 pp- to the total peak intensity observed at about 19 to 22 pp- is 0.83, Mll/MW is 2.1, and the bending stiffness degree is 1950kg/d, tensile yield strength is 10
5kg/cj, elongation is 695χ, Izod impact strength is 78.2.3.3 (23℃, -10℃, respectively) kg
-cm/c-, and the haze was 24%.

Example 7 Using an autoclave with an internal volume of 21, the catalyst of Example 1 was similarly dissolved in 11 of toluene, and 13k of propylene was heated at 30°C.
g/d-G was inserted, then 68 g of hexene-1 was injected, propylene was added so that the polymerization pressure was 3 kg/cd-G, and polymerization was carried out for 1 hour. After 11 minutes, unreacted monomer was purged and the polymer was inserted into a large amount of methanol.
Then, the powder obtained by filtration was diluted with 1 l of methanol.
After washing twice, it was dried under reduced pressure at 80°C to obtain 80g of polymer. According to C-NMR analysis, it contained 14.3wtχ (7.7molχ) of hexene-1, and the peak intensity observed at about 20.2pp- was approximately 19%.
The ratio of the peak intensity observed in the ~22pp garden to the total was 0.79. η is 1.18 and MW/M
N was 3.9. This powder was molded in the same way and its physical properties were measured.The zero bending rigidity was 1800 kg/C-1, the tensile yield strength was 88 kg/d, the elongation was 753χ, and the Izot impact strength was 78.9.3.0 (respectively at 23°C, -10'
C) kg-cm/c-, and the haze was 23%.

Example 8 Internal volume 5j! 1500g of propylene in an autoclave
300 g of 1-hexene-l was injected under pressure, then a catalyst was inserted in the same manner as in Example 2, and the mixture was stirred at 30°C for 1 hour. After purging unreacted propylene, the powder was taken out, dispersed in 500 m of hexane, and filtered at 40°C. , further 500m
The resulting product was washed three times with hexane and then dried under reduced pressure at 80° C. to obtain 160 g of syndiotactic polypropylene. Physical properties were measured in the same manner as in Example 1, and η was 1.1.
8, hexene-1 content 6.9wtX (3.6 mol2),
About 19-2 of the peak intensity observed at about 20.2 ppm
The ratio of the peak strength observed in 29PII to the total is 0.85, MW/MN is 2.1, the stiffness is 2600 kg/cj, and the tensile yield strength is 121 kg/C.
11l, elongation is 680χ, Izot impact lI strength is 48
．． 5.3.0 (23℃, -10℃, respectively) kg-c
m/cm, and the haze was 28%.

Example 9 A purified product obtained by recrystallizing isopropyl (cyclopentadienyl-l-fluorenyl) zirconium dichloride obtained in Example 1 in an autoclave with an internal volume of 21 and a degree of polymerization of 1
The same procedure as in Example 1 was used except that methylaluminoxane No. 6 was used, but it was dissolved in toluene 11, and 40 g of butene-1 and 170 g of propylene were added, followed by 23 g of ethylene, and polymerized at 20"C for 30 minutes. After polymerization, unreacted monomers were purged, a large amount of methanol was added, and the resulting powder was washed twice with methanol 11 and then washed with 80 ml of methanol.
It was dried under reduced pressure at .degree. C. to obtain 78 g of polymer. Eye C-NM
When analyzed by R, the ethylene content was 8.6wtX
(12.8 mol2>, butene-1 content is 12.9HH (
The ratio of the peak intensity observed at about 9.6 m/m and about 20.2 pp- to the total peak intensity observed at about 19 to 2299 m was 0.55. Also, η is 0.78
and the interval/MN was 2.5. This powder was molded in the same manner and its physical properties were measured. Tensile yield strength mackerel 49kg/
d, the growth is 137! , eye shift impact strength is 28.7
6 (23°C and -10°C, respectively), and the haze was 18z.

Example 1O 650 g of propylene was placed in an autoclave with contents of $151.
butene-1 60. , 4G of ethylene, and the catalyst of Example 2 were similarly pressurized at 30°C. After stirring at 30°C for 30 minutes, and then purging unreacted propylene, the powder was taken out, dispersed in 50M hexane, filtered at 40°C, and washed three times with 500-hexane.
It was dried under reduced pressure at 0°C to obtain 295 g of syndiotactic polypropylene.

When physical properties were measured in the same manner as in Example 1, η was 0092,
Ethylene content 5.5wtχ (8.2molχ), butene-
1 content 8.5wt! (6, Omore L4), approximately 20.2p
ps+ About 19 to 22 pp- of the observed peak intensity
The ratio of the peak intensity observed to the total sum is 0.62
and MW/MN was 2.1. This powder is also 7i! It was molded and its physical properties were measured. Tensile yield strength is 68
kg/d, elongation is 156χ, eye shift impact strength is 19
．． 48 (23°C and 110°C respectively) kg-cm/c
+s and the haze was 24.

Example 11 Example 1O except that hexene-1 was used instead of butene-1
In the same manner as above, 48 g of polymer was obtained.

``As analyzed by C-NMR, the ethylene content was 6.
．． 5wtX (9.7 mol, hexene-1 content is 4.8
wtX (2.3 mol χ), about 20.2 p, the ratio of the peak intensity observed at about 19 to 22 pp- to the total peak intensity was 0.61. Also, η
is 0.54, and M11/? IN was 2.5.

The physical properties of the 1-zono sheet similarly obtained using this powder were as follows: tensile yield strength was 87 kg/cj, and elongation was 177x.
, Izod impact strength is 26.58 (23℃,
-10℃) kg-cs+/cs+, haze is 1
It was 2χ.

Example 12 The procedure of Example 9 was repeated except that 4-methylpentene-1 was used instead of butene-1, and 41 g of polymer was obtained.

``As analyzed by C-NMR, the ethylene content was 6.
．． 2 wt
Approximately 19 to 22 ppm+ of the peak intensity observed in ppm
The ratio of the peak intensity observed to the total sum is 0.65
Met. Also, η is 0.43, and MW/MN is 2
．． It was 2. 1 obtained in the same manner using this powder
The tensile yield strength of the mm sheet is 92 kg/cti.
The elongation was 163L, the Izod impact strength was 24.55 (23°C1-1o''C, respectively) kg-ClI/c11, and the haze was 14χ.

〔Effect of the invention〕

The copolymer of the present invention has excellent physical properties and is extremely valuable industrially.

Claims (1)

[Claims] The intensity of the peak observed at about 20.2 ppm measured by ^1^3C-NMR is 0.3 or more of the intensity of the peak attributed to the methyl group of all propylene units, and is 0.1 to 3
A syndiotactic polypropylene copolymer containing 0 mol% of olefins other than propylene.